EP0446689B1 - Coloured pigments which are stable in glaze - Google Patents
Coloured pigments which are stable in glaze Download PDFInfo
- Publication number
- EP0446689B1 EP0446689B1 EP91102640A EP91102640A EP0446689B1 EP 0446689 B1 EP0446689 B1 EP 0446689B1 EP 91102640 A EP91102640 A EP 91102640A EP 91102640 A EP91102640 A EP 91102640A EP 0446689 B1 EP0446689 B1 EP 0446689B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- oxide
- metal
- pigments according
- pigments
- glazes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000049 pigment Substances 0.000 title claims description 27
- 239000000758 substrate Substances 0.000 claims description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims description 14
- 150000004706 metal oxides Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000010445 mica Substances 0.000 claims description 10
- 229910052618 mica group Inorganic materials 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000007900 aqueous suspension Substances 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 230000000485 pigmenting effect Effects 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 9
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- 229910016876 Fe(NH4)2(SO4)2 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
- C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/10—Interference pigments characterized by the core material
- C09C2200/1054—Interference pigments characterized by the core material the core consisting of a metal
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
- C09C2200/40—Interference pigments comprising an outermost surface coating
- C09C2200/401—Inorganic protective coating
Definitions
- the invention relates to glaze-stable color pigments based on platelet-shaped substrates coated with metal oxides, which are stable in decorative colors, engobes, glazes and enamels.
- platelet-shaped pigments coated with metal oxide which contain alkaline earth metal oxide or hydroxide in the outer coating.
- glaze-stable color pigments are obtained when coating platelet-shaped substrates in such a way that the coating is free from alkaline earth metal and silicon oxide, contains a colored metal oxide or metal hydroxide and at least 10% by weight aluminum oxide, and that the ratio of colored metal oxide or metal hydroxide to aluminum oxide 10 is up to 0.5 to 1.
- the pigments produced according to US Pat. No. 4,435,220 are far less resistant to color and heat, for example when frits are incorporated. While the colors already change at around 850 ° C, the pigments according to the invention remain color-stable at least up to 1000 ° C.
- EP 0082984 describes pearlescent pigments based on mica flakes coated with titanium dioxide, the outer metal oxide layer being a homogeneous mixed layer composed of titanium dioxide, silicon dioxide and iron oxide. Because of their high titanium dioxide content, the titanium dioxide mica pigments described there are not suitable for use in glazes, since they are not heat-resistant.
- the invention therefore relates to color pigments with improved stability in decorative colors, engobes, glazes and enamels on the basis of platelet-shaped substrates coated with metal oxide, characterized in that the outer coating is free from alkaline earth metal oxide, from at least one colored metal oxide or metal hydroxide, aluminum oxide and optionally titanium. or zinc oxide, the proportion of aluminum oxide being at least 10% by weight and the ratio of colored metal oxide or metal hydroxide to aluminum hydroxide being 10 to 0.5 to 1.
- the invention further relates to a process for the preparation of the pigments according to the invention, in which an aqueous suspension of a platelet-shaped substrate is mixed with a solution of an aluminum salt and at least one salt of a metal, the oxide of which is colored and optionally a titanium or zinc salt and a base, which in this way, the substrate coated with hydroxides or hydrated oxides is separated, optionally washed and dried, and then calcined.
- the invention also relates to the use of the pigments according to the invention for pigmenting glazes and enamels.
- the invention finally relates to materials coated with glazes or enamels, which contain the pigments according to the invention.
- any platelet-shaped materials such as mica, talc, kaolin, glass or metal platelets or platelet-shaped metal oxides, and mica flakes already coated with metal hydroxides or oxides, in particular titanium dioxide, can be used as platelet-shaped substrates.
- mica flakes are used as substrates, the particle size range is approximately 1-100 »m, preferably 5-50» m. Mica flakes ⁇ 15 »m are particularly preferred.
- the metal platelets those are suitable which do not yet melt at the high application temperatures.
- the particle size of other platelet-shaped substrates is generally in the same range as that specified for the mica flakes. However, if special effects are to be achieved, the average particle sizes can also lie outside the ranges mentioned.
- the substrates are mixed in aqueous suspension with a solution of an aluminum and at least one further metal salt.
- metal salts include iron, cobalt and chromium salts such as FeSO4, FeCl2, Fe (NH4) 2 (SO4) 2, Fe (NO3) 2, Fe2 (SO4) 3, FeCl3, FeNH4 (SO4) 2, Fe (NO3) 3, CoCl3, CoSO4, Co (NO3) 2, CrCl3, Cr2 (SO4) 3 and CrNH4 (SO4) 2 preferred.
- the aluminum salts for example Al2 (SO4) 3, AlNH4 (SO4) 2, AlCl3, Al (NO3) 3, AlNa (SO4) 2 and AlK (SO4) 2 are suitable. If necessary, suitable salt solutions of other metals such as zinc or titanium can be added.
- the ratio of the metal salts to one another can be varied within wide limits.
- the metal salts can also be used in the form of their hydrates.
- the aluminum salt content must in any case be selected so that the coating of the finished pigment according to the invention contains at least 10% by weight of aluminum oxide.
- the metal salt hydrolysis is carried out according to methods known per se, e.g. in DE 35 35 818 or that described in EP 0 077 959.
- a 5-25% by weight suspension of the platelet-shaped substrate in the solution of the metal salts which contains about 0.2 to 1.2 mmol of metal salts per square meter of substrate surface to be coated, is produced.
- the pH value is kept largely constant by simultaneously metering in a base.
- a pH value suitable for hydrolysis is usually around 1-7.
- Suitable bases are, for example, alkali metal solutions such as sodium hydroxide solution or potassium hydroxide solution or else aqueous ammonia, and also other bases, for example described in EP 0 077 959.
- the base is added as an about 5 to 35% solution.
- the salts are hydrolyzed and the metals are deposited in the form of their hydroxides or oxide hydrates.
- the substrates coated in this way are then separated off, dried at approximately 120 ° C. and calcined at approximately 400 ° to 950 ° C.
- pigments according to the invention preference is given to those which essentially contain one or two further metal oxides in the coating in addition to aluminum oxide.
- the aluminum oxide content in the coating is preferably 10 to 70% by weight, in particular 15 to 35% by weight.
- Coatings with a high iron oxide content in addition to aluminum oxide in a ratio of approximately 10 to 0.5: 1, in particular approximately 3.5 to 2.5: 1, are very particularly preferred.
- the pigments according to the invention can be used for all known applications, but owing to the improved stability, they are preferably used for pigmenting ceramic materials and in silicate flows.
- Example 2 The procedure is analogous to Example 1, but with a changed Fe / Al ratio. The following are used: 111.5 g FeCl3 x 6 H2O and 23.9 g Al2 (SO4) 3 x 18 H2O.
- Example 2 The procedure is analogous to Example 1, but with a changed Fe / Al ratio. The following are used: 111.5 g FeCl3 x 6 H2O and 215.4 g Al2 (SO4) 3 x 18 H2O.
- the procedure is analogous to Example 1, but with a changed Fe / Al ratio.
- the salt solution is additionally mixed with an aqueous TiCl4 solution (400 g / l). Amounts used: 45.7 g FeCl3 x 6 H2O, 58.8 g Al2 (SO4) 3 x 18 H2O, 80.1 ml TiCl4 solution.
- Example 1 1 g of a pigment produced according to Example 1 is mixed with 4 g of a ground, commercially available decorative color frit and 6 g of the screen printing medium Degussa 80840 (from Degussa) and ground again in a centrifugal ball mill. This mixture is applied to a piece of glass using the screen printing process (61 T screen fabric). It is then fired at 850 ° C for 5 minutes. A shiny decorative layer with a red-orange color is obtained.
- Example 5 The procedure is analogous to Example 5 and fired at 850 °, 950 ° and 1000 ° C, but a 120 T sieve fabric is used. Shiny, color-stable decorative layers with orange color are obtained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
Die Erfindung betrifft glasurstabile Farbpigmente auf der Basis von mit Metalloxiden beschichteten plättchenförmigen Substraten, die in Dekorfarben, Engoben, Glasuren und Emails stabil sind.The invention relates to glaze-stable color pigments based on platelet-shaped substrates coated with metal oxides, which are stable in decorative colors, engobes, glazes and enamels.
Es sind zahlreiche Pigmente bekannt, die in Glasuren, Emails oder vergleichbaren Materialien eingearbeitet werden. Sie sind jedoch mit einer Reihe von Nachteilen behaftet. So sind viele von ihnen bei den üblichen Einbrennbedingungen von etwa 700°-800 °C nicht temperaturstabil, da sie von den aggressiven Schmelzflüssen stark angegriffen werden. Andere wiederum enthalten einen hohen Anteil von umweltbelastenden Schwermetallen, z.B. Cadmium, um eine stabile Färbung, z.B. im gelben und roten Farbbereich zu gewährleisten.Numerous pigments are known which are incorporated into glazes, enamels or comparable materials. However, they have a number of disadvantages. For example, many of them are not temperature stable under the usual baking conditions of around 700 ° -800 ° C, as they are severely attacked by the aggressive melt flows. Others contain a high proportion of polluting heavy metals, e.g. Cadmium to ensure a stable color, e.g. guarantee in the yellow and red color range.
Es bestand demnach ein Bedürfnis nach Pigmenten, die die erwähnten Nachteile nicht oder nur noch in geringem Maße besitzen.Accordingly, there was a need for pigments which do not have the disadvantages mentioned or only have them to a small extent.
Aus der US-Patentschrift 4,435,220 sind mit Metalloxid beschichtete, plättchenförmige Pigmente bekannt, die in der Außenbeschichtung Erdalkalimetalloxid oder-hydroxid enthalten.From US Pat. No. 4,435,220, platelet-shaped pigments coated with metal oxide are known which contain alkaline earth metal oxide or hydroxide in the outer coating.
Überraschenderweise wurde gefunden, daß man glasurstabile Farbpigmente erhält, wenn man plättchenförmige Substrate derart beschichtet, daß die Beschichtung erdalkalimetall- und siliziumoxidfrei ist, ein farbiges Metalloxid oder Metallhydroxid und mindestens 10 Gew.% Aluminiumoxid enthält und daß das Verhältnis farbiges Metalloxid oder Metallhydroxid zu Aluminiumoxid 10 bis 0,5 zu 1 beträgt.Surprisingly, it was found that glaze-stable color pigments are obtained when coating platelet-shaped substrates in such a way that the coating is free from alkaline earth metal and silicon oxide, contains a colored metal oxide or metal hydroxide and at least 10% by weight aluminum oxide, and that the ratio of colored metal oxide or metal hydroxide to aluminum oxide 10 is up to 0.5 to 1.
Im Vergleich zu den erfindungsgemäßen Pigmenten zeigt sich, daß die nach US-Patentschrift 4,435,220 hergestellten Pigmente beispielsweise beim Einarbeiten von Fritten weit weniger farb- und hitzebeständig sind. Während sich die Farben bereits teilweise bei etwa 850°C verändern, bleiben die erfindungsgemäßen Pigmente mindestens bis 1000°C farbstabil.In comparison with the pigments according to the invention, it can be seen that the pigments produced according to US Pat. No. 4,435,220 are far less resistant to color and heat, for example when frits are incorporated. While the colors already change at around 850 ° C, the pigments according to the invention remain color-stable at least up to 1000 ° C.
In der EP 0082984 werden Perlglanzpigmente auf Basis von mit Titandioxid beschichteten Glimmerschuppen beschrieben, wobei die äußere Metalloxidschicht eine homogene Mischschicht aus Titandioxid, Siliziumdioxid und Eisenoxid ist. Die dort beschriebenen Titandioxidglimmerpigmente sind aufgrund ihres hohen Titandioxidgehalts für die Verwendung in Glasuren nicht geeignet, da sie nicht hitzebeständig sind.EP 0082984 describes pearlescent pigments based on mica flakes coated with titanium dioxide, the outer metal oxide layer being a homogeneous mixed layer composed of titanium dioxide, silicon dioxide and iron oxide. Because of their high titanium dioxide content, the titanium dioxide mica pigments described there are not suitable for use in glazes, since they are not heat-resistant.
Gegenstand der Erfindung sind daher Farbpigmente mit einer verbesserten Stabilität in Dekorfarben, Engoben, Glasuren und Emails auf der Basis von mit Metalloxid beschichteten plättchenförmigen Substraten, dadurch gekennzeichnet, daß die Außenbeschichtung erdalkalimetalloxidfrei ist, aus mindestens einem farbigen Metalloxid oder Metallhydroxid, Aluminiumoxid und gegebenenfalls Titan- oder Zinkoxid besteht, wobei der Anteil an Aluminiumoxid mindestens 10 Gew% beträgt und das Verhältnis farbiges Metalloxid oder Metallhydroxid Zu Aluminiumhydroxid 10 bis 0,5 zu 1 beträgt.The invention therefore relates to color pigments with improved stability in decorative colors, engobes, glazes and enamels on the basis of platelet-shaped substrates coated with metal oxide, characterized in that the outer coating is free from alkaline earth metal oxide, from at least one colored metal oxide or metal hydroxide, aluminum oxide and optionally titanium. or zinc oxide, the proportion of aluminum oxide being at least 10% by weight and the ratio of colored metal oxide or metal hydroxide to aluminum hydroxide being 10 to 0.5 to 1.
Gegenstand der Erfindung ist weiterhin ein Verfahren zur Herstellung der erfindungsgemäßen Pigmente, wobei man eine wäßrige Suspension eines plättchenförmigen Substrates mit einer Lösung eines Aluminiumsalzes und mindestens eines Salzes eines Metalls, dessen Oxid gefärbt ist und gegebenenfalls eines Titan- oder Zinksalzes und einer Base vermischt, das auf diese Weise mit Hydroxiden bzw. Oxidhydraten beschichtete Substrat abtrennt, gegebenenfalls wäscht und trocknet, und dann kalziniert.The invention further relates to a process for the preparation of the pigments according to the invention, in which an aqueous suspension of a platelet-shaped substrate is mixed with a solution of an aluminum salt and at least one salt of a metal, the oxide of which is colored and optionally a titanium or zinc salt and a base, which in this way, the substrate coated with hydroxides or hydrated oxides is separated, optionally washed and dried, and then calcined.
Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen Pigmente zur Pigmentierung von Glasuren und Emails.The invention also relates to the use of the pigments according to the invention for pigmenting glazes and enamels.
Gegenstand der Erfindung sind schließlich mit Glasuren oder Emails überzogene Materialien, die die erfindungsgemäßen Pigmente enthalten.The invention finally relates to materials coated with glazes or enamels, which contain the pigments according to the invention.
Als plättchenförmige Substrate können im Prinzip beliebige plättchenförmige Materialien wie Glimmer, Talk, Kaolin, Glas- oder Metallplättchen oder plättchenförmige Metalloxide, sowie bereits mit Metallhydroxiden oder -oxiden, insbesondere Titandioxid, beschichtete Glimmerschuppen eingesetzt werden. Werden Glimmerschuppen als Substrate eingesetzt, so beträgt der Teilchengrößenbereich etwa 1-100 »m, vorzugsweise 5-50 »m. Insbesondere bevorzugt sind Glimmerschuppen < 15 »m. Von den Metallplättchen sind diejenigen geeignet, die bei den hohen Anwendungstemperaturen noch nicht schmelzen.In principle, any platelet-shaped materials such as mica, talc, kaolin, glass or metal platelets or platelet-shaped metal oxides, and mica flakes already coated with metal hydroxides or oxides, in particular titanium dioxide, can be used as platelet-shaped substrates. If mica flakes are used as substrates, the particle size range is approximately 1-100 »m, preferably 5-50» m. Mica flakes <15 »m are particularly preferred. Of the metal platelets, those are suitable which do not yet melt at the high application temperatures.
Die Teilchengröße anderer plättchenförmiger Substrate liegt in der Regel im gleichen, wie für die Glimmerschuppen angegebenen Bereich. Sollen jedoch spezielle Effekte erzielt werden, so können die durchschnittlichen Teilchengrößen auch außerhalb der genannten Bereiche liegen.The particle size of other platelet-shaped substrates is generally in the same range as that specified for the mica flakes. However, if special effects are to be achieved, the average particle sizes can also lie outside the ranges mentioned.
Die Substrate werden in wäßriger Suspension mit einer Lösung eines Aluminium- und mindestens eines weiteren Metallsalzes vermischt. Von den Metallsalzen sind Eisen-, Kobalt- und Chromsalze wie FeSO₄, FeCl₂, Fe(NH₄)₂(SO₄)₂, Fe(NO₃)₂, Fe₂(SO₄)₃, FeCl₃, FeNH₄(SO₄)₂, Fe(NO₃)₃, CoCl₃, CoSO₄, Co(NO₃)₂, CrCl₃, Cr₂(SO₄)₃ und CrNH₄(SO₄)₂ bevorzugt. Von den Aluminiumsalzen sind beispielsweise Al₂(SO₄)₃, AlNH₄(SO₄)₂, AlCl₃, Al(NO₃)₃, AlNa(SO₄)₂ und AlK(SO₄)₂ geeignet. Falls erforderlich können noch geeignete Salzlösungen anderer Metalle wie bespielsweise von Zink oder Titan zugesetzt werden. Das Verhältnis der Metallsalze miteinander ist in weiten Grenzen variierbar. Die Metallsalze sind dabei auch in Form ihrer Hydrate einsetzbar. Der Aluminiumsalzanteil ist auf jeden Fall so zu wählen, daß die erfindungsgemäße Beschichtung des fertiggestellten Pigments mindestens 10 Gew.% Aluminiumoxid enthält.The substrates are mixed in aqueous suspension with a solution of an aluminum and at least one further metal salt. Of the metal salts are iron, cobalt and chromium salts such as FeSO₄, FeCl₂, Fe (NH₄) ₂ (SO₄) ₂, Fe (NO₃) ₂, Fe₂ (SO₄) ₃, FeCl₃, FeNH₄ (SO₄) ₂, Fe (NO₃) ₃, CoCl₃, CoSO₄, Co (NO₃) ₂, CrCl₃, Cr₂ (SO₄) ₃ and CrNH₄ (SO₄) ₂ preferred. Of the aluminum salts, for example Al₂ (SO₄) ₃, AlNH₄ (SO₄) ₂, AlCl₃, Al (NO₃) ₃, AlNa (SO₄) ₂ and AlK (SO₄) ₂ are suitable. If necessary, suitable salt solutions of other metals such as zinc or titanium can be added. The ratio of the metal salts to one another can be varied within wide limits. The metal salts can also be used in the form of their hydrates. The aluminum salt content must in any case be selected so that the coating of the finished pigment according to the invention contains at least 10% by weight of aluminum oxide.
Die Metallsalzhydrolyse wird nach an sich bekannten Verfahren, wie z.B. in der DE 35 35 818 oder der in der EP 0 077 959 beschrieben, durchgeführt.The metal salt hydrolysis is carried out according to methods known per se, e.g. in DE 35 35 818 or that described in EP 0 077 959.
In der Regel wird eine 5-25 Gew.%ige Suspension des plättchenförmigen Substrats in der Lösung der Metallsalze, die etwa 0,2 bis 1,2 mmol Metallsalze pro qm zu beschichtender Substratoberfläche enthält, hergestellt. Durch gleichzeitiges Zudosieren einer Base wird der pH-Wert weitgehend konstant gehalten. Ein zur Hydrolyse geeigneter pH-Wert liegt in der Regel bei etwa 1-7. Als Basen sind z.B. Alkalilaugen wie Natronlauge oder Kalilauge oder auch wäßriger Ammoniak, sowie andere, beispielsweise in der EP 0 077 959 beschriebene Basen geeignet. Die Base wird als etwa 5 bis 35%ige Lösung zugegeben. Die Salze werden dabei hydrolysiert und die Metalle in Form ihrer Hydroxide oder Oxidhydrate abgeschieden. Die so beschichteten Substrate werden anschließend abgetrennt, bei etwa 120 °C getrocknet und bei etwa 400° bis 950 °C kalziniert.As a rule, a 5-25% by weight suspension of the platelet-shaped substrate in the solution of the metal salts, which contains about 0.2 to 1.2 mmol of metal salts per square meter of substrate surface to be coated, is produced. The pH value is kept largely constant by simultaneously metering in a base. A pH value suitable for hydrolysis is usually around 1-7. Suitable bases are, for example, alkali metal solutions such as sodium hydroxide solution or potassium hydroxide solution or else aqueous ammonia, and also other bases, for example described in EP 0 077 959. The base is added as an about 5 to 35% solution. The salts are hydrolyzed and the metals are deposited in the form of their hydroxides or oxide hydrates. The substrates coated in this way are then separated off, dried at approximately 120 ° C. and calcined at approximately 400 ° to 950 ° C.
Von den erfindungsgemäßen Pigmenten sind diejenigen bevorzugt, die in der Beschichtung neben Aluminiumoxid im wesentlichen ein oder zwei weitere Metalloxide enthalten. Der Aluminiumoxidgehalt in der Beschichtung beträgt vorzugsweise 10 bis 70 Gew.%, insbesondere 15 bis 35 Gew.%.Of the pigments according to the invention, preference is given to those which essentially contain one or two further metal oxides in the coating in addition to aluminum oxide. The aluminum oxide content in the coating is preferably 10 to 70% by weight, in particular 15 to 35% by weight.
Ganz besonders bevorzugt sind Beschichtungen mit einem hohen Eisenoxidanteil neben Aluminiumoxid im Verhältnis von etwa 10 bis 0,5 : 1, insbesondere von etwa 3,5 bis 2,5 : 1.Coatings with a high iron oxide content in addition to aluminum oxide in a ratio of approximately 10 to 0.5: 1, in particular approximately 3.5 to 2.5: 1, are very particularly preferred.
Um die gewünschte Stabilisierung zu erreichen, sind substantielle Mengen dieser Oxide aufzubringen. Es hat sich als zweckmäßig erwiesen, die erfindungsgemäße Beschichtung in Mengen von etwa 5 bis 75 Gew.%, bezogen auf das Gesamtpigment, aufzubringen.In order to achieve the desired stabilization, substantial amounts of these oxides have to be applied. It has proven to be expedient to apply the coating according to the invention in amounts of about 5 to 75% by weight, based on the total pigment.
Die erfindungsgemäßen Pigmente können im Prinzip für alle bekannten Anwendungen eingesetzt werden, aufgrund der verbesserten Stabilität finden sie jedoch vorzugsweise Anwendung bei der Pigmentierung von keramischen Materialien und in silikatischen Flüssen.In principle, the pigments according to the invention can be used for all known applications, but owing to the improved stability, they are preferably used for pigmenting ceramic materials and in silicate flows.
100 g Glimmer mit einer Teilchengröße < 15 »m werden in 2 l vollentsalztem (VE)-Wasser suspendiert. Durch Zugabe von verdünnter Salzsäure wird ein pH-Wert von 5,5 eingestellt. 152,1 g FeCl₃ x 6 H₂O und 93,8 g Al₂(SO₄)₃ x 18 H₂O werden in VE-Wasser gelöst. Die Lösung wird auf ein Volumen von 1,5 l aufgefüllt. Anschließend wird die Fe/Al-Salzlösung zur Glimmersuspension gegeben, wobei durch Zugabe einer 10%igen Natronlauge der pH-Wert bei 5,5 gehalten sind. Es werden verschiedene Proben abgenommen, und zwar nach Zugabe folgender Mengen an Salzlösung:
- a) 600 ml
- b) 675 ml
- c) 750 ml
- d) 850 ml
- e) 1000 ml
- f) 1200 ml
- a) 600 ml
- b) 675 ml
- c) 750 ml
- d) 850 ml
- e) 1000 ml
- f) 1200 ml
Es wird analog Beispiel 1 gearbeitet, jedoch mit verändertem Fe/Al-Verhältnis. Es werden eingesetzt: 111,5 g FeCl₃ x 6 H₂O und 23,9 g Al₂(SO₄)₃ x 18 H₂O.The procedure is analogous to Example 1, but with a changed Fe / Al ratio. The following are used: 111.5 g FeCl₃ x 6 H₂O and 23.9 g Al₂ (SO₄) ₃ x 18 H₂O.
Es wird analog Beispiel 1 gearbeitet, jedoch mit verändertem Fe/Al-Verhältnis. Es werden eingesetzt: 111,5 g FeCl₃ x 6 H₂O und 215,4 g Al₂(SO₄)₃ x 18 H₂O.The procedure is analogous to Example 1, but with a changed Fe / Al ratio. The following are used: 111.5 g FeCl₃ x 6 H₂O and 215.4 g Al₂ (SO₄) ₃ x 18 H₂O.
Es wird analog Beispiel 1 gearbeitet, jedoch mit verändertem Fe/Al-Verhältnis. Die Salzlösung wird zusätzlich mit einer wäßrigen TiCl₄-Lösung (400 g/l) vermischt. Eingesetzte Mengen:
45,7 g FeCl₃ x 6 H₂O, 58,8 g Al₂(SO₄)₃ x 18 H₂O, 80,1 ml TiCl₄-Lösung.The procedure is analogous to Example 1, but with a changed Fe / Al ratio. The salt solution is additionally mixed with an aqueous TiCl₄ solution (400 g / l). Amounts used:
45.7 g FeCl₃ x 6 H₂O, 58.8 g Al₂ (SO₄) ₃ x 18 H₂O, 80.1 ml TiCl₄ solution.
1 g eines nach Beispiel 1 hergestellten Pigments wird mit 4 g einer gemahlenen, im Handel erhältlichen Dekorfarbenfritte und 6 g des Siebdruckmediums Degussa 80840 (Fa. Degussa) vermischt und in einer Fliehkraftkugelmühle nochmals vermahlen. Diese Mischung wird im Siebdruckverfahren auf einen Scherben aufgetragen (61 T Siebgewebe). Anschließend wird bei 850 °C 5 min lang gebrannt. Man erhält eine glänzende Dekorschicht mit rot-oranger Farbe.1 g of a pigment produced according to Example 1 is mixed with 4 g of a ground, commercially available decorative color frit and 6 g of the screen printing medium Degussa 80840 (from Degussa) and ground again in a centrifugal ball mill. This mixture is applied to a piece of glass using the screen printing process (61 T screen fabric). It is then fired at 850 ° C for 5 minutes. A shiny decorative layer with a red-orange color is obtained.
Analog werden weitere Scherben bedruckt und bei 950° und bei 1000 °C gebrannt. Die Färbung bleibt dabei weitgehend unverändert.Analogously, other fragments are printed and fired at 950 ° and 1000 ° C. The color remains largely unchanged.
Es wird analog Beispiel 5 verfahren und jeweils auch bei 850°, 950° und 1000 °C gebrannt, allerdings wird ein 120 T Siebgewebe verwendet. Man erhält glänzende, farbstabile Dekorschichten mit oranger Farbe.The procedure is analogous to Example 5 and fired at 850 °, 950 ° and 1000 ° C, but a 120 T sieve fabric is used. Shiny, color-stable decorative layers with orange color are obtained.
Claims (6)
- Colour pigments having an improved stability in decorative colours, engobes, glazes and enamels, based on platelet-type substrates coated with metal oxides, characterized in that the outer coating is free from alkaline earth metal oxides and consists of at least one coloured metal oxide or metal hydroxide, aluminium oxide and optionally titanium or zinc oxide, the proportion of aluminium oxide being at least 10% by weight and the ratio of coloured metal oxide or metal hydroxide to aluminium hydroxide being 10 to 0.5 : 1.
- Pigments according to Claim 1, characterized in that the coating consists essentially of iron oxide and aluminium oxide.
- Pigments according to Claims 1 or 2, characterized in that mica flakes are used as substrate.
- Process for the production of pigments according to at least one of Claims 1 to 3, characterized in that an aqueous suspension of a platelet-type substrate is mixed with a solution of an aluminium salt and at least one salt of a metal whose oxide is coloured, and optionally of a titanium or zinc salt and a base, the substrate coated in this manner with hydroxides or hydrated oxides is separated, if appropriate, washed, dried and then calcined.
- Use of pigments according to at least one of Claims 1 to 3 for pigmenting glazes and enamels.
- Materials coated with glazes or enamels, characterized in that they contain pigments according to at least one of the Claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4007037A DE4007037A1 (en) | 1990-03-07 | 1990-03-07 | Glaze-stable color pigments |
| DE4007037 | 1990-03-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0446689A1 EP0446689A1 (en) | 1991-09-18 |
| EP0446689B1 true EP0446689B1 (en) | 1995-12-06 |
Family
ID=6401539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91102640A Expired - Lifetime EP0446689B1 (en) | 1990-03-07 | 1991-02-22 | Coloured pigments which are stable in glaze |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5106419A (en) |
| EP (1) | EP0446689B1 (en) |
| JP (1) | JP3336019B2 (en) |
| KR (1) | KR910016876A (en) |
| AU (1) | AU7268391A (en) |
| BR (1) | BR9100909A (en) |
| CS (1) | CS51291A2 (en) |
| DE (2) | DE4007037A1 (en) |
| ES (1) | ES2079499T3 (en) |
| FI (1) | FI911132A7 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0608388B1 (en) * | 1991-10-18 | 1998-07-08 | MERCK PATENT GmbH | Coloured and coated platelike pigments |
| CA2136736A1 (en) * | 1992-06-08 | 1993-12-23 | Harry C. Mcdaniel | Luster pigment application methods |
| IT1256263B (en) * | 1992-12-30 | 1995-11-29 | Bayer Italia Spa | GRANULATES OF SLIDING DYES, CHEMICALLY RESISTANT, THEIR PREPARATION AND THEIR USE |
| DE19516960A1 (en) * | 1995-05-12 | 1996-11-14 | Merck Patent Gmbh | Color pigments |
| US5783506A (en) * | 1997-01-31 | 1998-07-21 | Engelhard Corporation | Ceramic glaze including pearlescent pigment |
| FR2761056A1 (en) * | 1997-03-18 | 1998-09-25 | Joseph Gascon | Coating slip for application to ceramic material |
| JP3911315B2 (en) * | 1997-03-19 | 2007-05-09 | メルク株式会社 | High saturation orange pearl pigment |
| KR100529446B1 (en) * | 1997-03-19 | 2006-01-27 | 메르크 파텐트 게엠베하 | High-chroma orange pearl pigment |
| US6190445B1 (en) | 1998-03-05 | 2001-02-20 | Merck Patent Gesellschaft | High-chroma orange pearl pigment |
| DE19859420A1 (en) * | 1998-12-22 | 2000-06-29 | Merck Patent Gmbh | Modified pearlescent engobe |
| RU2270176C2 (en) * | 2004-04-01 | 2006-02-20 | Институт физико-химических проблем керамических материалов Российской академии наук (ИПК РАН) | Method for production of ammonium alum-based pigments |
| DE102009023497B4 (en) | 2009-06-02 | 2012-04-19 | Nanogate Ag | Glaze composition with glass plates of various sizes, process for their preparation, process for the production of glazed sanitary ware and use of the glaze composition |
| EP3046974B1 (en) * | 2013-09-19 | 2024-10-30 | Sun Chemical B.V. | Non-magnetizable effect pigments |
| ES2926748A1 (en) * | 2021-04-19 | 2022-10-27 | Torrecid Sa | METHOD FOR PRODUCING DECORATED CERAMIC TILES WITH PROTECTION OF THE CHROMATIC EFFECTS DERIVED FROM THE CERAMIC PIGMENTS AND RESULTING CERAMIC TILES ACCORDING TO THE METHOD |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE759469A (en) * | 1969-11-29 | 1971-05-26 | Merck Patent Gmbh | PEARL GLOSS PIGMENT AND THEIR METHODS OF |
| JPS5876461A (en) * | 1981-10-26 | 1983-05-09 | メルク・パテント・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Transparent coloring pigment and manufacture |
| DE3151355A1 (en) * | 1981-12-24 | 1983-07-07 | Merck Patent Gmbh, 6100 Darmstadt | "PEARL SHINE PIGMENTS WITH IMPROVED LIGHT RESISTANCE, THEIR PRODUCTION AND USE" |
| DE3617430A1 (en) * | 1986-05-23 | 1987-11-26 | Merck Patent Gmbh | PEARL PIGMENT |
| EP0282329B1 (en) * | 1987-03-11 | 1992-01-29 | Tayca Corporation | Titanium dioxide coated micaceous iron oxide pigments and method for producing the same |
| US4959090A (en) * | 1988-09-28 | 1990-09-25 | Ciba-Geigy Corporation | Glass enamel coating compositions |
-
1990
- 1990-03-07 DE DE4007037A patent/DE4007037A1/en not_active Withdrawn
-
1991
- 1991-02-22 EP EP91102640A patent/EP0446689B1/en not_active Expired - Lifetime
- 1991-02-22 ES ES91102640T patent/ES2079499T3/en not_active Expired - Lifetime
- 1991-02-22 DE DE59107003T patent/DE59107003D1/en not_active Expired - Fee Related
- 1991-02-27 CS CS91512A patent/CS51291A2/en unknown
- 1991-03-05 JP JP06249391A patent/JP3336019B2/en not_active Expired - Fee Related
- 1991-03-06 AU AU72683/91A patent/AU7268391A/en not_active Abandoned
- 1991-03-06 BR BR919100909A patent/BR9100909A/en not_active Application Discontinuation
- 1991-03-06 FI FI911132A patent/FI911132A7/en not_active Application Discontinuation
- 1991-03-07 US US07/665,859 patent/US5106419A/en not_active Expired - Lifetime
- 1991-03-07 KR KR1019910003627A patent/KR910016876A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| ES2079499T3 (en) | 1996-01-16 |
| KR910016876A (en) | 1991-11-05 |
| EP0446689A1 (en) | 1991-09-18 |
| FI911132L (en) | 1991-09-08 |
| BR9100909A (en) | 1991-11-05 |
| DE4007037A1 (en) | 1991-09-12 |
| DE59107003D1 (en) | 1996-01-18 |
| AU7268391A (en) | 1991-10-03 |
| JP3336019B2 (en) | 2002-10-21 |
| CS51291A2 (en) | 1991-09-15 |
| FI911132A0 (en) | 1991-03-06 |
| JPH04214084A (en) | 1992-08-05 |
| FI911132A7 (en) | 1991-09-08 |
| US5106419A (en) | 1992-04-21 |
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